Nanomaterial-based catalytic conversion of hazardous organic pollutants into benign substances is one of the green methods employed for wastewater treatment. This study demonstrates the fabrication of (rGO-ZnO)/CuO nanocomposites (NCs) via a microwave (MW)-assisted method for (photo)catalytic application. The crystal structure, optical, morphological, and electrochemical characteristics were examined using X-ray diffraction (XRD), spectroscopic, microscopic, and electrochemical techniques. The analysis indicated that rod-like (rGO-ZnO)/CuO NCs having a nanoscale diameter with enhanced light absorption and well-matched band positions between rGO-ZnO and CuO were formed. Furthermore, the catalytic reduction of 4-nitrophenol (4-NP) and photocatalytic degradation of methylene blue (MB) tests showed remarkable results with rate constants of 0.468 min⁻¹ for 4-NP reduction within 8 min and 0.02213 min⁻¹ for MB degradation within 105 min. Thus, the artful decoration of ZnO nanorods (NRs) with CuO into the (rGO-ZnO)/CuO NCs interface is an effective strategy for fabricating highly efficient photocatalysts.